US8080180B2 - Preparation of stable silver colloids - Google Patents

Preparation of stable silver colloids Download PDF

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Publication number
US8080180B2
US8080180B2 US12/294,151 US29415107A US8080180B2 US 8080180 B2 US8080180 B2 US 8080180B2 US 29415107 A US29415107 A US 29415107A US 8080180 B2 US8080180 B2 US 8080180B2
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Prior art keywords
silver
mixture
particle size
predetermined temperature
lithium citrate
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US20090236570A1 (en
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Peter Cyril White
Jakob Howie Hjortkjaer
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University of Lincoln
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University of Lincoln
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0043—Preparation of sols containing elemental metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes

Definitions

  • the present invention concerns methods of making stable silver colloids and to colloids produced by the method.
  • the colloids are especially useful for Raman spectroscopy.
  • a colloid is a suspension of the metal particles in solution.
  • controlled aggregation of the silver colloid particles is required, typically using inorganic (e.g. chloride or nitrate) or organic (e.g. poly-L-lysine or spremine) compounds as aggregation reagents.
  • the colloidal silver particles should be about 20-50 nm, prior to aggregation, and have a narrow particle size distribution.
  • SERS surface enhanced Raman scattering
  • SERRS surface enhanced resonance Raman scattering
  • Silver colloids can be prepared by chemical reduction with either sodium borohydride or sodium citrate. Citrate reduced colloids are more stable and many analysts have prepared these using a method published by P. C. Lee and O. Meisel (J. Phys. Chem., 1982, 86, 3391-3395). Batch to batch reproducibility is difficult to achieve by this method and the stability, i.e. shelf life, is variable. Preparation requires the use of ultra clean glassware and accurately controlled temperatures, stirring speed, etc.
  • Silver colloids prepared according to these known prior methods produce silver particles with a negative citrate layer on their surface, and for maximum surface enhancement effects analytes must be in close proximity to the aggregated silver surface. For cationic analytes this can be achieved as they are attracted to the negatively charged silver surface. With anionic analytes only a very weak SER(R)S effect is achieved due to repulsion from the silver surface.
  • the authors of the modified colloid preparation method resolved this problem by using poly-L-lysine as the aggregation agent, but adding ascorbic acid to control pH and protonate the aggregating agent, which then acted as a bridge between the colloid surface and the analyte.
  • a method for producing a silver colloidal solution comprises reducing silver nitrate with lithium citrate.
  • the invention also provides a silver colloid solution made by reducing silver nitrate with lithium citrate.
  • the method preferably includes the steps of (a) heating a first quantity of water to a first predetermined temperature; (b) adding a second quantity of silver nitrate to the water; (c) heating the mixture to a second predetermined temperature; (d) adding a third quantity of an aqueous lithium citrate solution to the mixture; (e) maintaining the mixture at the second predetermined temperature for a predetermined time; and (f) cooling the mixture.
  • the mixing process is conveniently carried out in a three-necked container.
  • the first predetermined temperature is 45° C.
  • the second predetermined temperature is 98° C.
  • the first quantity is 500 ml of high purity water
  • the second quantity is 90 mg of silver nitrate of 99.99:99% purity
  • the third quantity is 10 ml of aqueous lithium citrate solution
  • the aqueous lithium citrate solution comprises 227 mg of lithium citrate in 25 ml high purity water
  • the water and the mixture are stirred constantly throughout steps (a) to (f).
  • the predetermined time is preferably 90 minutes.
  • FIG. 1 is the UV/visible spectrum showing stability of a silver colloid produced by a method in accordance with the invention
  • FIG. 2 is a graph showing particle size analyses of lithium and sodium citrate sliver colloids.
  • FIG. 3 is a graph of Raman intensity against wave number comparing a lithium citrate and a sodium citrate silver colloid used for the SERRS analysis of Rhodamine 6G.
  • Lithium heads the Group 1 elements and displays some very different properties to sodium. Lithium is very electropositive and, as a result of its small atomic radius, has a high electrostatic charge and hence high salvation energy. Additionally, lithium compounds tend to form covalent as opposed to ionic bonds and, furthermore, lithium is much larger compared to sodium when hydrated. It was therefore considered by the Applicant that these properties could provide smaller particle size silver colloids and better stability in containers made of various different materials, which had proved troublesome in the past.
  • High purity water 500 ml-BDH; 18 m ⁇ was put in a three-necked, one litre, round-bottomed flask.
  • a thermometer (range 0-110° C.) was held in one of the side necks of the flask. Whilst stirring, the water temperature was raised and, on reaching 45° C., silver nitrate (90 mg-99.9999%; Aldrich Chemicals) was added through the third neck of the flask. The temperature of the contents of the flask was raised quickly to 98° C. and then 10 ml of aqueous lithium citrate solution (227 mg in 25 ml BDH high purity water) was added to the reaction mixture.
  • the resulting silver colloidal solution exhibits a narrow size distribution, and is highly stable in glass and a wide range of other polymeric container materials, In addition, the silver colloidal solution exhibits high light-scattering properties and particularly intense SERS and SERRS spectra with very low fluorescence background levels.
  • the silver colloidal solution can be aggregated with either organic or inorganic aggregating reagents of the kind used in Raman spectroscopy. Above all, the silver colloidal solution is incredibly stable and has a long shelf life.
  • FIG. 1 shows a graph of the UV/visible spectrum of a silver colloid prepared by the method described.
  • UV/visible spectroscopy provides a method for characterisation of the silver colloid. Measurement of band width at half peak height gives an indication of the particle size distribution of the colloid particles—more uniform particle size leads to the narrower band width. Values of typically 60-70 nm are obtained for sodium citrate reduced colloids, and these give reasonable SERRS properties, but with lithium citrate reduced colloids below 60 nm have been obtained.
  • the band width for the example described is 46 nm.
  • the ⁇ max value is related to the particle size distribution and scattering properties of the colloid. Colloids with a value of 390-400 nm have been found to give the best SERRS properties, and with sodium citrate reduced colloids it is often difficult to achieve below 400 nm; the typical range is 400-410 nm. The ⁇ max value for the example described is 399 nm.
  • FIG. 1 also shows that there is virtually no change in the spectroptometric properties over a period of 5 months, thus indicating the stability of silver colloids produced according to the invention. Batches of these colloids have found to be stable over this extended period in glass and containers made of polymeric materials including, high and low density polyethylene, polypropylene and polyethylene terephthalate.
  • Particle size analysis of a silver colloid produced in accordance with the invention as shown in FIG. 2 indicate that, in comparison with a silver colloid produced by the method described in the prior art, the former has a narrower distribution of particles of smaller with similar mean particle size (4 nm compared with 4.5 nm) but with no significant number of particles greater than 11 nm.
  • the sodium citrate silver colloid shows another distribution of particles in the range of 18-23 nm, The differences observed here account for the higher absorbance value, lower bandwidths and lower ⁇ max values observed in the visible spectra of lithium citrate silver colloids ie., a larger number of smaller colloidal silver particles with a more uniform particle size being produced.
  • the silver colloid solution produced in accordance with the invention does produce intense SERS and SERRS spectra.
  • Rhodamine 6G a dye standard commonly used for assessing SERFS activity of colloids
  • a colloid should be able to produce strong SERRS spectra from a 10 ⁇ 9 M solution of the dye by using an aggregating agent which is either inorganic, such as sodium chloride, or organic, for example poly-L-lysine.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Composite Materials (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Molecular Biology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Colloid Chemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US12/294,151 2006-03-23 2007-03-21 Preparation of stable silver colloids Expired - Fee Related US8080180B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0605752.5A GB0605752D0 (en) 2006-03-23 2006-03-23 Preparation of stable silver colloids
GB0605752.5 2006-03-23
PCT/GB2007/050138 WO2007107792A1 (en) 2006-03-23 2007-03-21 Preparation of stable silver colloids

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US20090236570A1 US20090236570A1 (en) 2009-09-24
US8080180B2 true US8080180B2 (en) 2011-12-20

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US (1) US8080180B2 (de)
EP (1) EP2007513B1 (de)
JP (1) JP5417659B2 (de)
AT (1) ATE461743T1 (de)
DE (1) DE602007005465D1 (de)
DK (1) DK2007513T3 (de)
ES (1) ES2343594T3 (de)
GB (1) GB0605752D0 (de)
WO (1) WO2007107792A1 (de)

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GB0724870D0 (en) * 2007-12-21 2008-01-30 Univ Lincoln The Preparation of metal colloids
US7846866B2 (en) 2008-09-09 2010-12-07 Guardian Industries Corp. Porous titanium dioxide coatings and methods of forming porous titanium dioxide coatings having improved photocatalytic activity
US8647652B2 (en) * 2008-09-09 2014-02-11 Guardian Industries Corp. Stable silver colloids and silica-coated silver colloids, and methods of preparing stable silver colloids and silica-coated silver colloids
US8545899B2 (en) 2008-11-03 2013-10-01 Guardian Industries Corp. Titanium dioxide coatings having roughened surfaces and methods of forming titanium dioxide coatings having roughened surfaces
RU2456356C1 (ru) 2011-04-29 2012-07-20 Борис Сергеевич Кустов Коллоидный раствор наносеребра и способ его получения
KR20130035014A (ko) * 2011-09-29 2013-04-08 삼성전기주식회사 금속 입자의 제조방법, 이를 이용하여 제조된 잉크 조성물 및 페이스트 조성물
CN106442466A (zh) * 2016-11-09 2017-02-22 南京理工大学 一种氧化石墨烯辅助的sers活性基底表面清洁方法
JP7190277B2 (ja) * 2018-07-31 2022-12-15 浜松ホトニクス株式会社 被検体分析方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853464A (en) * 1996-05-10 1998-12-29 Ciba Specialty Chemicals Corporation Pigment compositions
US6051614A (en) * 1991-12-28 2000-04-18 Hidefumi Hirai Method for preparing a non-aqueous dispersion of particles of a metal and/or a metal compound
US20040234958A1 (en) * 2000-04-08 2004-11-25 Smith William Ewen Analyte detection and apparatus therefor
US20050142567A1 (en) * 2003-12-29 2005-06-30 Intel Corporation Composite organic-inorganic nanoparticles and methods for use thereof
US20050191665A1 (en) * 2003-12-29 2005-09-01 Xing Su Composite organic-inorganic nanoclusters
US20090233237A1 (en) * 2006-06-22 2009-09-17 Mitsubishi Paper Mills Limited Process For Preparing Conductive Material

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9517955D0 (en) * 1995-07-25 1995-11-08 Univ Strathclyde Nucleotide sequence detection and analysis
JP3429958B2 (ja) * 1996-08-28 2003-07-28 三井金属鉱業株式会社 銀コロイド液の製造方法
JP4424723B2 (ja) * 2003-07-07 2010-03-03 バンドー化学株式会社 導電性被膜複合体
CN1934438A (zh) * 2004-02-04 2007-03-21 英特尔公司 表面增强拉曼散射中使用锂盐的化学增强
WO2005082561A1 (ja) * 2004-02-27 2005-09-09 Sanc Salaam Corporation コロイダル金属
JP2006045655A (ja) * 2004-08-09 2006-02-16 Mitsubishi Materials Corp 銀ナノ粒子とその製造方法
JP2007194174A (ja) * 2006-01-23 2007-08-02 Seiko Epson Corp 導体パターン用インク、導体パターン、配線基板及び電気光学装置並びに電子機器

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051614A (en) * 1991-12-28 2000-04-18 Hidefumi Hirai Method for preparing a non-aqueous dispersion of particles of a metal and/or a metal compound
US5853464A (en) * 1996-05-10 1998-12-29 Ciba Specialty Chemicals Corporation Pigment compositions
US20040234958A1 (en) * 2000-04-08 2004-11-25 Smith William Ewen Analyte detection and apparatus therefor
US20050142567A1 (en) * 2003-12-29 2005-06-30 Intel Corporation Composite organic-inorganic nanoparticles and methods for use thereof
US20050147963A1 (en) * 2003-12-29 2005-07-07 Intel Corporation Composite organic-inorganic nanoparticles and methods for use thereof
US20050191665A1 (en) * 2003-12-29 2005-09-01 Xing Su Composite organic-inorganic nanoclusters
US20090233237A1 (en) * 2006-06-22 2009-09-17 Mitsubishi Paper Mills Limited Process For Preparing Conductive Material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
P.C. Lee and D. Meisel, "Adsorption and Surface-Enhanced Raman of Dyes on Silver and Gold Sols", J. Phys. Chem., 86, 1982, 3391-3395. *

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JP2009531547A (ja) 2009-09-03
WO2007107792A1 (en) 2007-09-27
US20090236570A1 (en) 2009-09-24
DE602007005465D1 (de) 2010-05-06
EP2007513A1 (de) 2008-12-31
JP5417659B2 (ja) 2014-02-19
DK2007513T3 (da) 2011-01-10
GB0605752D0 (en) 2006-05-03
ATE461743T1 (de) 2010-04-15
EP2007513B1 (de) 2010-03-24
ES2343594T3 (es) 2010-08-04

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